CN107799646B - Alloy thermoelectric semiconductor material and preparation method thereof - Google Patents
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- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
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Abstract
The invention relates to an alloy thermoelectric semiconductor material and a preparation method thereof, wherein the chemical formula of the alloy thermoelectric semiconductor material is (GeTe)1‑x(PbSe)xWherein x is more than 0 and less than or equal to 0.4; when in preparation, firstly, the single elements Ge, Te, Pb and Se are sequentially filled into a quartz ampoule from small to large according to the density, and then the quartz ampoule is vacuumized and packaged, and then the steps of melt quenching, annealing quenching and hot-pressing sintering are sequentially carried out, and finally the quartz glass is prepared. Compared with the prior art, the invention realizes the large-range regulation and control of the carrier concentration by respectively carrying out the replacement of the elements (Ge/Pb, Te/Se) in the same main group on the positions of anions and cations in the GeTe material, thereby achieving the optimized carrier concentration level of the GeTe material, simultaneously increasing the thermoelectric figure of merit of the material by the point defect introduced by the element replacement, greatly reducing the lattice thermal conductivity of the material while regulating the carrier concentration, and providing a new idea for improving the thermoelectric performance of the GeTe-based thermoelectric material and similar materials thereof.
Description
Technical Field
The invention relates to the technical field of new energy materials, in particular to an alloy thermoelectric semiconductor material and a preparation method thereof.
Background
The conventional fossil fuels on the earth are continuously reduced, meanwhile, the problems of environmental pollution and energy crisis are increasingly prominent, and the requirement of cleaning renewable energy is urgent. The thermoelectric material can realize the interconversion of heat and electricity, and can be used as a generator or a refrigerator based on the Seebeck effect or the Peltier effect. The working medium in the thermoelectric material is a carrier inherent to the material, so that the thermoelectric material can be used as a noise-free, zero-emission and environment-friendly direct energy conversion tool and plays an important role in the aspect of utilization of industrial waste heat and automobile exhaust waste heat.
The energy conversion efficiency of thermoelectric materials is usually measured by a dimensionless thermoelectric figure of merit, zT ═ S2σ T/κ, wherein: t is the absolute temperature, S is the Seebeck coefficient; σ is the conductivity; kappa is the thermal conductivity, from electron thermal conductivity kappaEAnd lattice thermal conductivity κLTwo parts are formed. Seebeck coefficient S, electric conductivity sigma, and electronic thermal conductivity kappaEStrong coupling between three parameters, there areThe method for effectively decoupling the parameters and improving the thermoelectric performance of the material has the functions of increasing the degeneracy of energy bands, reducing energy bands, improving the effective quality and weakening the scattering effect. By reducing the unique independent parameter, the lattice thermal conductivity κLMethods for improving thermoelectric figure of merit include: forming point defects of nano structure, liquid phonon, vacancy, interstitial atom and the like, and increasing lattice non-harmonic vibration.
The above method for improving thermoelectric figure of merit of the material firstly ensures that the carrier concentration of the material is within the optimized carrier concentration interval because of the power factor (S) of the thermoelectric material2σ) and thermoelectric figure of merit (zT) can only be maximized over a narrow carrier concentration range. The carrier concentration required for optimal electrical performance has temperature and band structure dependence, and a common method for regulating the carrier concentration is to carry out doping by replacing an aliovalent element. However, this method is often limited by the limited solubility of the doping element in the matrix, and the low doping level not only makes it difficult to achieve a wide range of carrier concentrations, but also introduces a small number of point defects that do not reduce the lattice thermal conductance of the matrix material to a very low level. For p-type GeTe material, a great deal of cation vacancies exist inherently, so that the p-type GeTe material has very high carrier concentration, and the regulation of the carrier concentration and the achievement of an optimized level through chemical doping are relatively difficult.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an alloy thermoelectric semiconductor material and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
an alloy thermoelectric semiconductor material with a chemical formula of (GeTe)1-x(PbSe)xWherein x is more than 0 and less than or equal to 0.4.
Preferably, the value range of x is 0.2-0.3, and at the moment, the carrier concentration can be better optimized.
Preferably, the value range of x is 0.25-0.4, and the lattice thermal conductivity is relatively excellent.
More preferably, x is 0.27.
A method of making an alloy thermoelectric semiconductor material, preferably comprising the steps of:
(1) and (3) vacuum packaging:
elemental elements Ge, Te, Pb and Se with the purity of more than 99.99 percent are proportioned according to the stoichiometric ratio, and are sequentially filled into a quartz ampoule from small to large according to the density, and the ampoule is vacuumized and then packaged;
(2) melting and quenching:
placing the quartz ampoule in a well type furnace for heating, enabling the raw materials to react in a molten state, and then quenching to obtain a first ingot;
(3) annealing and quenching:
then placing the first ingot in a well type furnace for heating, annealing at high temperature, and quenching again to obtain a second ingot;
(4) hot-pressing and sintering:
and grinding the second ingot into powder, placing the powder in a graphite mold, carrying out vacuum hot-pressing sintering, and cooling to obtain a flaky block material, namely the alloy thermoelectric semiconductor material.
Further preferably, in step (2):
the heating and reaction process is as follows: heating the quartz ampoule to 900-1000 ℃ from room temperature at the speed of 150-200 ℃/h, and preserving the heat for 6-12 hours. More preferably, the temperature rise rate is 200 ℃/h and the holding temperature is 950 ℃.
Further preferably, in step (3):
the heating and high-temperature annealing process specifically comprises the following steps: heating the quartz ampoule from room temperature to 550-600 ℃ at the speed of 150-200 ℃/h, and preserving the temperature for 2-4 days. More preferably, the heating rate is 200 ℃/h, the holding temperature is 600 ℃, and the holding time is 3 days.
Further preferably, in the step (4), the vacuum hot-pressing sintering process specifically includes: under the vacuum condition, the temperature is increased to 550-600 ℃ at the speed of 100-300 ℃/min, the pressure is adjusted to 50-70 MPa, and the treatment is carried out for 40min at constant temperature and constant pressure. More preferably, in the step (4), the sintering temperature is raised to 587 ℃ and the pressure for sintering is 60 MPa.
Further preferably, in the step (4), the cooling process specifically includes: cooling to room temperature at a rate of 20-30 deg.C/min.
More preferably, the absolute vacuum degree of the vacuum in the step (1), the step (3) and the step (4) is not more than 10-1Pa。
According to the invention, the GeTe material is used as a substrate, and the carrier concentration is optimized by a method of forming a solid solution with the same main group material PbSe, increasing cations and reducing the average size of anions, so that the lattice thermal conductivity is reduced, and the thermoelectric property of the GeTe base material is improved. The large-size Pb atoms replace the cations Ge of the GeTe, and the small-size Se atoms replace the anions Te of the GeTe, so that the average size of the cations of the GeTe base material is increased, the average size of the anions of the GeTe base material is reduced, the formation of cation vacancies is further reduced, and the carrier concentration is reduced. Meanwhile, a large number of point defects are introduced by replacing a large number of atoms on the positions of anions and cations, atomic mass and stress imbalance are formed in GeTe crystal lattices, and the scattering effect on phonons is enhanced, so that the crystal lattice thermal conductivity of the GeTe matrix material is reduced. The work not only proves that the GeTe material is an excellent thermoelectric material, but also provides a method for improving the performance of the same material.
Compared with the prior art, the invention has the following advantages:
(1) for the P type GeTe base material with high carrier concentration caused by vacancy, the average size of cations is increased through the replacement of cation positions, the size of cations is increased through the replacement of anion positions, and the carrier concentration range is regulated through the reduction of anion size.
(2) By solid dissolving 0-40% (atomic percent) of PbSe in GeTe matrix, the carrier concentration realizes 7 multiplied by 1019～8×1020cm-3Fine control in the range and reach the optimized carrier concentration level of the GeTe matrix material.
(3) The introduced point defects reduce the lattice thermal conductivity of the GeTe base material by 75 percent when the main group element Pb replaces Ge and Se replaces Te.
(4) The carrier concentration optimization and the crystal lattice thermal conductance are simultaneously reduced, the thermoelectric figure of merit reaches 2.2 when 800K, the average thermoelectric figure of merit is improved by 300% when 300K-800K, and a method is provided for improving the thermoelectric performance of GeTe-based thermoelectric materials and similar materials.
Drawings
FIG. 1 shows solid solutions (GeTe) of different compositions1-x(PbSe)xXRD pattern of (a);
FIG. 2 shows solid solutions (GeTe) of different compositions1-x(PbSe)xA relation graph of the Hall carrier concentration and the solid solution component;
FIG. 3 shows solid solutions (GeTe) of different compositions1-x(PbSe)xSeebeck coefficient (S) and Hall mobility (μ) of the sampleH) A plot of Hall carrier concentration;
FIG. 4 shows solid solutions (GeTe) of different compositions1-x(PbSe)xThe Seebeck coefficient (S), the electrical resistivity (p), the thermal conductivity (k), the lattice thermal conductivity (k)L) Temperature dependence;
FIG. 5 shows solid solutions (GeTe) of different compositions1-x(PbSe)xIs plotted against the doping composition;
FIG. 6 shows solid solutions (GeTe) of different compositions1-x(PbSe)xRoom temperature lattice thermal conductivity (κ)L) Experimental values and theoretical prediction plots of the relationship with doping composition;
FIG. 7 shows solid solutions (GeTe) of different compositions1-x(PbSe)xA thermoelectric figure of merit versus temperature graph of;
FIG. 8 shows solid solutions (GeTe) of different compositions1-x(PbSe)xA relationship between the average thermoelectric figure of merit (300 to 800K) and the solid solution component.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
A GeTe base alloy semiconductor thermoelectric material has a chemical formula of (GeTe)1-x(PbSe)xX is more than 0 and less than or equal to 0.4. In this example, x is 0.05, 0.15, 0.2, 0.23, 0.25, 0.27, 0.3, 0.35, and 0.4 (when x is 0, the chemical formula is GeTe, and when x is 0.05, 0.15, 0.2, 0.23, 0.25, 0.27, 0.3, 0.35, and 0.4, the carrier concentration is controlled by solid solution of different concentrations of PbSe, and the lattice thermal conductivity is reduced), and the amount of PbSe is adjusted according to the concentration of PbSeThe following preparation method was used to obtain (GeTe) with different carrier concentrations1-x(PbSe)xBulk material:
(1) according to the formula (GeTe) taking different x values1-x(PbSe)xWeighing elemental raw materials of germanium Ge, tellurium Te, lead Pb and selenium Se with the purity of more than 99.99% according to the stoichiometric ratio of (x is 0-0.4), placing the raw materials in a quartz ampoule, and packaging the quartz ampoule under vacuum.
(2) Suspending the quartz tube containing the raw materials in a high-temperature well type furnace, slowly heating to 900-1000 ℃ at the rate of 150-200 ℃ per hour, preserving heat for 6-12 hours, and then rapidly quenching and cooling to obtain a first ingot; this step of this example was performed by slowly raising the temperature to 950 ℃ at a rate of 200 ℃ per hour and holding the temperature at 950 ℃ for 6 hours.
(3) Carrying out heat treatment on the first ingot subjected to high-temperature melting quenching obtained in the step (2), slowly heating to 550-600 ℃ at the rate of 150-200 ℃ per hour, preserving heat for 2-4 days, and then rapidly quenching and cooling to obtain a second ingot; this step of this example was performed by slowly raising the temperature to 600 ℃ at a rate of 200 ℃ per hour and holding the temperature for 3 days.
(4) Grinding the second ingot obtained in the step (3) into powder, placing the powder in a graphite mold, heating to 550-600 ℃ at the rate of 100-300 ℃ per minute by using induction heating, adjusting the pressure to 50-70 MPa, keeping the temperature for 40min, performing vacuum high-temperature hot-pressing sintering, and then slowly cooling to room temperature at the rate of 20-30K/min to obtain (GeTe)1-x(PbSe)xA sheet of bulk material; in the step of this embodiment, the temperature is raised to 587 ℃ at a rate of 200 ℃ per minute, the pressure is adjusted to 60MPa, the temperature is kept for 40min, vacuum high-temperature hot-pressing sintering is performed, and then the product is slowly cooled to room temperature at a rate of 25K/min.
GeTe based solid solution (GeTe)1-x(PbSe)xThe XRD pattern of the substrate can be seen in figure 1, and the crystal structure of the substrate is not changed after the anions Ge and Te are respectively replaced by Pb and Se. The relation between the Hall carrier concentration and the PbSe content can be seen in figure 2, the Hall carrier concentration is continuously reduced along with the increase of the PbSe content, and when the PbSe content reaches 23-30 percent, the Hall carrier concentrationis-2X 1020cm-3The optimized carrier concentration interval of GeTe is reached. Seebeck coefficient (S) increases with decreasing carrier concentration at room temperature, and Hall mobility (μ) at room temperatureH) Decreases with decreasing carrier concentration, see in particular fig. 3.
Of different composition (GeTe)1-x(PbSe)xThe Seebeck coefficient (S), the electrical resistivity (p), the thermal conductivity (k), the lattice thermal conductivity (k)L) The variation with temperature can be seen in fig. 4. In the test temperature range, the seebeck coefficient (S), the resistivity (ρ) increases with increasing temperature, showing the properties of a degenerate semiconductor, the thermal conductivity (κ) decreases with increasing temperature. With the increase of the solid solution amount of PbSe, the concentration of Hall current carriers is reduced, the Fermi level is reduced, the Seebeck coefficient (S) and the resistivity (rho) are increased, and meanwhile, anions and cations replace introduced point defects, so that the scattering of phonons is enhanced to ensure the thermal conductivity (kappa)L) The reduction is 75%, see fig. 4. According to the Debye model, the interaction between phonons and phonons, the stress and strain caused by point defects, and the decrease in sound velocity at room temperature (see FIG. 5), at room temperature for (GeTe) with the increase in PbSe solid solution content were considered1-x(PbSe)xThe theoretical prediction of lattice thermal conductivity of the system is consistent with the experimental data points, see fig. 6. Finally, due to the increase of the size of the cations, the reduction of the size of the anions and the reduction of the vacancy concentration, the carrier concentration of the GeTe thermoelectric material is regulated and controlled to an optimal level, due to the introduction of a large number of point defects, the lattice thermal conductance is reduced by 75%, the thermoelectric figure of merit of the material reaches 2.2 after 800K, and the average thermoelectric figure of merit is increased by 300%, as shown in figure 7 and figure 8.
Example 2
The preparation method of the embodiment specifically comprises the following steps:
a preparation method of a high-performance GeTe-based alloy thermoelectric semiconductor material comprises the following steps:
(1) and (3) vacuum packaging: elemental elements Ge, Te, Pb and Se with the purity of more than 99.99 percent are proportioned according to the stoichiometric ratio, are sequentially filled into a quartz ampoule from small to large according to the density, are vacuumized for 30min by a mechanical pump and are packaged;
(2) melting and quenching: the quartz ampoule filled with the raw material was put into a shaft furnace and slowly heated, the quartz ampoule was heated from room temperature to 900 ℃ at a rate of 150 ℃ per hour and kept warm for 12 hours to react the raw material in a molten state, followed by quenching with cold water to obtain a first ingot.
(3) Annealing and quenching: the first ingot in the quartz ampoule is put into a well type furnace to be heated slowly, high-temperature annealing is carried out (specifically, the quartz tube is heated to 550 ℃ from room temperature at the rate of 150 ℃ per hour and is kept warm for 4 days), and then quenching is carried out to obtain a second ingot.
(4) Hot-pressing and sintering: and grinding the obtained second ingot into powder by using an agate mortar, placing the powder in a graphite mold, heating to 550 ℃ at the speed of 100 ℃ per minute by utilizing induction heating, adjusting the pressure to 50MPa, carrying out constant-temperature and constant-pressure treatment for 40min, carrying out vacuum hot-pressing sintering, and then slowly cooling to room temperature at the speed of 20 ℃ per minute to obtain the flaky block material, namely the high-performance GeTe-based thermoelectric material.
The absolute vacuum degree of the vacuum in the step (1), the step (3) and the step (4) is not more than 10-1Pa。
Example 3
The preparation method of the embodiment specifically comprises the following steps:
a preparation method of a high-performance GeTe-based alloy thermoelectric semiconductor material comprises the following steps:
(1) and (3) vacuum packaging: elemental elements Ge, Te, Pb and Se with the purity of more than 99.99 percent are proportioned according to the stoichiometric ratio, are sequentially filled into a quartz ampoule from small to large according to the density, are vacuumized for 30min by a mechanical pump and are packaged;
(2) melting and quenching: the quartz ampoule filled with the raw material is put into a well type furnace to be heated slowly, the quartz ampoule is heated up to 1000 ℃ from room temperature at the rate of 200 ℃ per hour and is kept warm for 6 hours, so that the raw material is reacted in a molten state, and then the raw material is quenched with cold water to obtain a first ingot.
(3) Annealing and quenching: the first ingot in the quartz ampoule is put into a well type furnace to be heated slowly, high-temperature annealing is carried out (specifically, the quartz tube is heated to 600 ℃ from room temperature at the rate of 200 ℃ per hour and is kept warm for 2 days), and then quenching is carried out to obtain a second ingot.
(4) Hot-pressing and sintering: and grinding the obtained second ingot into powder by using an agate mortar, placing the powder in a graphite mold, heating to 600 ℃ at the rate of 300 ℃ per minute by utilizing induction heating, adjusting the pressure to 70MPa, carrying out constant-temperature and constant-pressure treatment for 40min, carrying out vacuum hot-pressing sintering, and then slowly cooling to room temperature at the rate of 30 ℃ per minute to obtain the flaky block material, namely the high-performance GeTe-based thermoelectric material.
The absolute vacuum degree of the vacuum in the step (1), the step (3) and the step (4) is not more than 10-1Pa。
Example 5
The preparation method of the embodiment specifically comprises the following steps:
a preparation method of a high-performance GeTe-based alloy thermoelectric semiconductor material comprises the following steps:
(1) and (3) vacuum packaging: elemental elements Ge, Te, Pb and Se with the purity of more than 99.99 percent are proportioned according to the stoichiometric ratio, are sequentially filled into a quartz ampoule from small to large according to the density, are vacuumized for 30min by a mechanical pump and are packaged;
(2) melting and quenching: the quartz ampoule filled with the raw material is put into a well type furnace to be heated slowly, the quartz ampoule is heated up to 950 ℃ from the room temperature at the rate of 180 ℃ per hour and is kept warm for 8 hours, so that the raw material is reacted in a molten state, and then the raw material is quenched with cold water to obtain a first ingot.
(3) Annealing and quenching: and (3) slowly heating the first ingot in the quartz ampoule in a well type furnace, carrying out high-temperature annealing (specifically, heating the quartz tube from room temperature to 580 ℃ at the rate of 180 ℃ per hour, and keeping the temperature for 3 days), and then quenching to obtain a second ingot.
(4) Hot-pressing and sintering: and grinding the obtained second ingot into powder by using an agate mortar, placing the powder in a graphite mold, heating to 575 ℃ at the speed of 200 ℃ per minute by utilizing induction heating, adjusting the pressure to 60MPa, carrying out constant-temperature and constant-pressure treatment for 40min, carrying out vacuum hot-pressing sintering, and then slowly cooling to room temperature at the speed of 25 ℃ per minute to obtain the flaky block material, namely the high-performance GeTe-based thermoelectric material.
Step (1), step (3) and step(4) The absolute vacuum degree of the vacuum is not more than 10-1Pa。
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. Alloy thermoelectric semiconductor material (GeTe)1-x(PbSe)xCharacterized in that the chemical formula is (GeTe)1-x(PbSe)xWherein x is 0.27.
2. An alloy thermoelectric semiconductor material (GeTe) as claimed in claim 11-x(PbSe)xThe preparation method is characterized by comprising the following steps:
(1) and (3) vacuum packaging:
elemental elements Ge, Te, Pb and Se with the purity of more than 99.99 percent are proportioned according to the stoichiometric ratio, and are sequentially filled into a quartz ampoule from small to large according to the density, and the ampoule is vacuumized and then packaged;
(2) melting and quenching:
placing the quartz ampoule in a well type furnace for heating, enabling the raw materials to react in a molten state, and then quenching to obtain a first ingot;
(3) annealing and quenching:
then placing the first ingot in a well type furnace for heating, annealing at high temperature, and quenching again to obtain a second ingot;
(4) hot-pressing and sintering:
grinding the second ingot into powder, placing the powder in a graphite mould, carrying out vacuum hot-pressing sintering, and cooling to obtain a flaky block material, namely the alloy thermoelectric semiconductor material (GeTe)1-x(PbSe)x。
3. An alloy thermoelectric semiconductor material (GeTe) according to claim 21-x(PbSe)xThe method for producing (2), characterized in that:
the heating and reaction process is as follows: heating the quartz ampoule to 900-1000 ℃ from room temperature at the speed of 150-200 ℃/h, and preserving the heat for 6-12 hours.
4. An alloy thermoelectric semiconductor material (GeTe) according to claim 21-x(PbSe)xThe method of (2), characterized in that, in the step (3):
the heating and high-temperature annealing process specifically comprises the following steps: heating the quartz ampoule from room temperature to 550-600 ℃ at the speed of 150-200 ℃/h, and preserving the temperature for 2-4 days.
5. An alloy thermoelectric semiconductor material (GeTe) according to claim 21-x(PbSe)xThe preparation method is characterized in that in the step (4), the vacuum hot-pressing sintering process specifically comprises the following steps: under the vacuum condition, the temperature is increased to 550-600 ℃ at the speed of 100-300 ℃/min, the pressure is adjusted to 50-70 MPa, and the treatment is carried out for 40min at constant temperature and constant pressure.
6. An alloy thermoelectric semiconductor material (GeTe) according to claim 51-x(PbSe)xThe preparation method is characterized in that in the step (4), the sintering temperature is raised to 587 ℃, and the sintering pressure is 60 MPa.
7. An alloy thermoelectric semiconductor material (GeTe) according to claim 21-x(PbSe)xThe preparation method is characterized in that in the step (4), the temperature reduction process specifically comprises the following steps: cooling to room temperature at a rate of 20-30 deg.C/min.
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| CN111086976B (en) * | 2019-11-28 | 2022-12-16 | 同济大学 | Rhombic germanium telluride based compound thermoelectric material with near-room-temperature high thermoelectric performance and preparation method thereof |
| CN112661122B (en) * | 2020-12-27 | 2022-11-18 | 同济大学 | Germanium telluride based thermoelectric material with high thermoelectric performance |
| CN112670395B (en) * | 2020-12-27 | 2022-12-16 | 同济大学 | Germanium telluride based thermoelectric single-leg device with high conversion efficiency and power density and preparation thereof |
| CN113421958B (en) * | 2021-05-11 | 2023-05-19 | 上海大学 | Thermoelectric compound BaCu 2 Se 2 Material and preparation method thereof |
| CN114890794A (en) * | 2022-05-24 | 2022-08-12 | 西安交通大学 | High-performance N-type PbSe thermoelectric material and preparation method thereof |
| CN115991603A (en) * | 2022-11-24 | 2023-04-21 | 安徽大学绿色产业创新研究院 | Preparation method of Cr/Te co-doped PbSe-based thermoelectric material |
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